Regular Issue

Vol. 51, No. 10, 1999

22 data found. 1 - 22 listed
Communication | Regular issue | Vol 51, No. 10, 1999, pp. 2301 - 2304
Published online:
DOI: 10.3987/COM-99-8672
Conversion of Allyl Aryl Selenides into Selenochroman Derivatives

Hitoshi Abe,* Natsuko Koshiba, Akira Yamasaki, and Takashi Harayama*

*Faculty of Pharmaceutical Science, Okayama University, 1-1-1 Tsushima-naka, Okayama 700-8530, Japan


Several allyl aryl selenides were prepared and examined their reactions with aluminum bromide to give selenochroman derivatives in high to moderate yields. A plausible mechanism of this reaction is also discussed.

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Communication | Regular issue | Vol 51, No. 10, 1999, pp. 2305 - 2309
Published online:
DOI: 10.3987/COM-99-8678
Products from a Novel Reaction of Di- hydropyrazines with Vichinaldiamines

Tadatoshi Yamaguchi,* Shigeru Ito, Yukiko Iwase, Kenji Watanabe, and Kazunobu Harano

*Department of Hygiene, Miyazaki Medical college, Kiyotake-cho, Miyazaki 889-1692, Japan


Dihydropyrazines such as 2,3-dihydro-5,6-dimethylpyrazine reacted with 1,2-diamines like ethylenediamine to form cis-tetraazadecalins (TADs) as crystalline products. The NMR spectra of the products in CDCl3 or CD3CN at -20 ~ -60°C exhibited the signals due to TAD. However, the NMR spectra at room temperature showed that the TAD had dissociated into its parent materials. Seven TADs were obtained by only a mixing operation at a low temperature.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2311 - 2320
Published online:
DOI: 10.3987/COM-99-8535
4-Alkylcarbonylmethylideneisoquinolines. A Synthetic and Mechanistic Study

Isabel Moreno, Raul SanMartin, Imanol Tellitu,and Esther Domínguez*

*Kimika Organikoa Saila, Zientzi Fakultatea, Euskal Herriko Unibertsitatea, Vasco, P.O. Box 644, 48080-Bilbao, Basque Country, Spain


An efficient preparation of 4-alkylcarbonylmethylideneisoquinoline derivatives via a modification of Jones oxidation and alkene acylation conditions is reported. In addition, evidence on the mechanism involved in the formation of 12-alkylbenzo[c]phenanthridines from 3-aryl-4-methylideneisoquinolines is presented.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2321 - 2333
Published online:
DOI: 10.3987/COM-99-8584
Chemistry of Indoles Carrying a Basic Function. Part IV. Synthesis of D-Nor- ergoline and Ergoline Ring by Stobbe Reaction

István Moldvai, Eszter Temesvári-Major, Eszter Gács-Baitz, Orsolya Egyed, Ágnes Gömöry, László Nyulászi, and Csaba Szántay*

*Institute of Chemistry, Chemical Research Center, Hungarian Academy of Sciences, H-1525 Budpest , P.O. Box 17, Hungary


Starting from Uhle’s ketone (2), pentacyclic lactone derivatives with D-norergoline ring (13 and 14) have been prepared by an unusual intramolecular Stobbe reaction of a succinic diester derivative (3a). The preparation of ergoline ring (1) itself was also achieved through modification of the reaction conditions.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2335 - 2342
Published online:
DOI: 10.3987/COM-99-8586
New Synthesis of Benzo[a]phenazines Based on Acid Promoted Ring Opening of the Benzotriazole Moiety

Alan R. Katritzky,* Abd El Rachman Ferwanah, Yasuhisa Matsukawa, Peter J. Steel, and Sergey N. Denisenko

*Center for Heterocyclic Compounds, Department of Chemistry, University of Florida, P. O. Box 117200, Gainesville, FL 32611-7200, U.S.A.


Syntheses of benzo[a]phenazines (6a-d) have been accomplished based on an acid promoted tandem benzotriazole ring-opening / ammonia extrusion procedure. Compounds (6a-d) are thus accessible directly from 3-(benzotriazol-1-yl)-1,4-diaryl-1-buten-4-ols (3a-d) in one-pot reaction sequences or from the intermediate 3,4-dihydronaphthalenes (4a-c). This constitutes a new type of benzotriazole ring transformation.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2343 - 2347
Published online:
DOI: 10.3987/COM-99-8591
Synthesis of a Novel 7,14β-Ethano-bridged Opiate

Han Yu, Lijuan Wang, Judith L. Flippen-Anderson, Xinrong Tian, Andrew Coop, and Kenner C. Rice*

*Laboratory of Medicinal Chemistry, National Institute of Diabetes Digestive and Kidney Diseases, National Institute of Health, Bldg.8, Rm. B1-23 Betheda, MD 20892-0815, U.S.A.


A novel 7, 14β-ethano-bridged opiate (1) was prepared from the known 14-alkenylcodeinone (3) in two steps. Selective reduction of the enone double bond of 3 followed by ozonolysis led to an aldehyde intermediate, which was cyclized in situ through an intramolecular aldol condensation to give the rigid hexacyclic derivative (1).

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2349 - 2365
Published online:
DOI: 10.3987/COM-99-8625
Metalation of Pyrazinethiocarboxamides. Metalation of Diazines XXVI

Corinne Fruit, Alain Turck, Nelly Plé, and Guy Quéguiner*

*Laboratoire de Chimie Organique Fine et Hétérocyclique(UPRES-A 6014), IRCOF, INSA, Université de Rouen, Place Emilae Blondel, BP 08,76131 Mont-Saint-Aignan Cedex, France


Some new pyrazinethiocarboxamides were synthesized and metalated with LTMP in tetrahydrofuran. The reaction of these lithio derivatives with various electrophiles gave access to a large range of 2,5-disubstituted pyrazines. This unexpected regioselectivity was established by application of gradient enhanced HMBC sequence for the observation of long range 1H-15N heteronuclear couplings at natural abundance.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2367 - 2376
Published online:
DOI: 10.3987/COM-99-8627
Rotameric Properties of Novel N-Acyl and N-Acyloxy Dimeric 4-Phenyl-1,4-dihydropyridines Derived from Developed Solid-State Synthesis

Andreas Hilgeroth,* Ute Baumeister, and Frank Heinemann

*Institute of Pharmaceutical Chemistry, Department of Pharmacy, Martin-Luther-University Halle-Wittenberg, Wolfgang-Langenbeck-Str. 4, 06120 Halle, Germany


Novel N-acyl and N-acyloxy dimeric 4-phenyl-1,4-dihydropyridines are given by solid-state photodimerization of their monomeric educts in excellent yields. The existence of rotamers was demonstrated by 1H NMR spectroscopical measurement at certain temperatures and additionally supported by X-Ray crystal structure analysis of centrosymmetrical cage-dimeric N-acetyl-3,5-dimethoxycarbonyl-4-phenyl-1,4-dihydropyridine (3b). Topochemical investigations by X-Ray crystal structure analysis prove the formation of anti-dimeric N-Boc-3,5-dimethoxycarbonyl-4-phenyl-1,4-dihydropyridine (4e) to be controlled by the nearest distance of potentially reacting double bonds with 3.667(3) Å.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2377 - 2384
Published online:
DOI: 10.3987/COM-99-8629
A Synthesis of 4-Quinolone-3-carboxylic Acids via Pyrolysis of N-Aryldioxopyrrolines

Kunihiko Mohri,* Akihiko Kanie, Yoshie Horiguchi, and Kimiaki Isobe

*Showa College of Pharmaceutical Sciences, 3-3165, Higashi-tamagawagakuen, Machida, Tokyo 194-8543, Japan


A synthesis of 4-quinolone-3-carboxylic acids (8) was achieved by pyrolysis of 4,5-dimethoxycarbonyl-1-aryl-1H-pyrrole-2,3-diones (3) followed by selective de-methoxycarbonylation of the resulting 2,3-dimethoxycarbonyl-4-quinolones (4) in excellent overall yields.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2385 - 2397
Published online:
DOI: 10.3987/COM-99-8632
Reaction of Quinoline N-Oxides with Alkyl- and Aryllithiums in the Presence of Oxidant

Yoshinobu Tagawa, Manami Nomura, Hiroyuki Yamashita, Yoshinobu Goto,* and Masatomo Hamana

*Faculty of Pharmaceutical Sciences, Fukuoka University, Nakamura, Jonan-ku, Fukuoka, 814-0180, Japan


Quinoline and some 4-substituted quinoline 1-oxides react with alkyl- and aryllithiums in the presence of an oxidant to afford 2-alkyl- and 2-arylquinoline 1-oxides in generally good yields. Among oxidants used, 9-fluorenone is most effective. On the other hand, quinaldine 1-oxide undergoes a base-induced electrophilic reaction with n-BuLi and 9-fluorenone to give 2-[(9-hydroxyfluoren-9-yl)methyl]quinoline 1-oxide.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2399 - 2406
Published online:
DOI: 10.3987/COM-99-8633
Synthesis of Furo[2,3-c]quinolin-4(5H)-ones

Krishna C. Majumdar,* Anup K. Kundu, and Paritosh Biswas

*Department of Chemistry, University of Kalyani, Kalyani-741 235, W. B., India


A number of 1-aryloxymethyl-3H-pyrano[2,3-c]quinolin-5(6H)-ones (4a-d, 4f-i) on heating in N,N-diethylaniline for 8 h underwent an unusual ring contraction to give 1-aryloxymethyl-2-methylfuro[2,3-c]quinolin-4(5H)-ones(5a-d, 5f-i) in 66-79 % yields.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2407 - 2413
Published online:
DOI: 10.3987/COM-99-8639
Thermal Ring Contraction of 3H-1,4-Benzodiazepines into Quinazolines

Mamoru Kaname, Takashi Tsuchiya, and Haruki Sashida*

*Faculty of Pharmaceutical Sciences, Hokuriku University, 3-Ho, Kanagawa machi, Kanazawa 920-1181, Japan


The thermolysis of the 5-methoxy- (11a-c) and 5-diethylamino-3H-1,4-benzodiazepines (14a-c) resulted in a ring transformation to give the 4-methoxy- (12a-c) and 4-diethylaminoquinazolines (15a-c), respectively. The mechanism of this ring contraction is also described.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2415 - 2421
Published online:
DOI: 10.3987/COM-99-8643
Convenient Synthesis of Cyclohexa[a]pyrrolo[2,1-b][3]benzazepine, a Cephalotaxus Alkaloid Analogue

Hitoshi Tanaka,* Mitsunobu Doi, Hiroshi Shimizu, and Hideo Etoh

*Faculty of Pharmacy, Meijo University, 150 Yagoto, Tempaku-ku, Nagoya, Aichi 468-8503, Japan


Irradiation of N-(3-hydroxy-4-methoxyphenethyl)-3-(2-iodo-5-methoxyphenyl)propionamide (11) in methanol in the presence of sodium hydroxide furnished 3-hydroxy-2,12-dimethoxy-6,7,9,10-tetrahydrodibenz-[d,f]azecin-8(5H)-one (14) which was successfully led to cephalotaxine analogue (17) bearing pyrrolo[2,1-b][3]benzazepine skeleton by reduction with borane followed by Birch reduction and subsequent acidic treatment. The structure of 17 was established by means of X-ray crystallography.

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Paper | Regular issue | Vol 51, No. 10, 1999, pp. 2423 - 2430
Published online:
DOI: 10.3987/COM-99-8649
tert-Butyl 2-{1-[2-Aryl-4-oxothiazol-5- (4H)-ylidene]ethyl}diazene-1-carboxyl- ates: A New Class of 1,2-Diaza-1,3- butadienes

Orazio A. Attanasi, Paolino Filippone,* Barbara Guidi, Francesca R. Perrulli, and Stefania Santeusanio

*Istituto di Chimica Organica, Facolta di Scienze, Università di Urbino, Piazza della Repubblica 13, I-61029 Urbino, Italy


The synthesis and reactions of tert-butyl 2-{1-[2-aryl-4-oxothiazol-5(4H)-ylidene]ethyl}diazene-1-carboxylates: a new class of 1,2-diaza-1,3-butadienes is reported.

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2431 - 2438
Published online:
DOI: 10.3987/COM-99-8624
Substituent Effects in the Ring-Chain Tautomerism of 1,2-Diarylimidazolidines

Anikó Göblyös, László Lázár, Ferenc Evanics, and Ferenc Fülöp*

*Institute of Pharmaceutical Chemistry, Abert Szent-Györgyi Medical University, POB 121, H-6701 Szeged, Eötvös u. 6, Hungary


1,2-Diaryl-substituted imidazolidines proved to be ring-chain tautomeric mixtures in CDCl3 at 300 K. Both 1- and 2-aryl groups exerted significant electronic effect on the tautomeric equilibria, which could be described by the equation log KX = ρσ+ + log KX=H.

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2439 - 2444
Published online:
DOI: 10.3987/COM-99-8631
Diastereoselective Synthesis of trans- 4-Arylpiperidine-3-carboxylic Acid Derivatives from 4-Aryl-1,4-dihydropyridine

Kae-Shyang Shih, Chin-Wei Liu, Yu-Jung Hsieh, Shyh-Fong Chen, Hao Ku, Lee Tai Liu,* Ya-Chuan Lin, Hsiang-Ling Huang, and Chia-Lin Jeff Wang

*Deparatment of Medicinal Chemistry, Development Center for Biotechnology, Hsi-Chih Research Park 102, Lane 169, Kang Ning St, Hsi Chih 221, Taipei Hsien, Taiwan, R.O.C.


A convenient procedure for the preparation of trans-3,4-disubstituted piperidines from 4-aryl-1,4-dihydropyridine is described. The diastereoselective synthesis of an unnatural amino acid, trans-4-arylpiperidine-3-carboxylic acid, and its derivatives is exemplified. The key steps include the construction of a trans-3,4-disubstituted piperidine moiety in compound (5), N-methyl carbamate of trans-4-aryl-piperidine-3-carboxylic acid, from 4-aryl-1,4-dihydropyridine-3-carboxylic acid methyl ester (2) via hydrogenation, reduction, and hydrolysis. Reduction of acid (5) with lithium aluminum hydride or with sodium borohydride provided the corresponding carbinol (7) or (8).

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2445 - 2451
Published online:
DOI: 10.3987/COM-99-8635
Synthesis of Trifluoromethylpyrimidines from Fluorinated En-aminodiketones

Mustapha Soufyane, Sarah van den Broek, Layachi Khamliche, and Catherine Mirand*

*Laboratoire de Transformations et Synthèse de Substances Naturelles, UPRESA/CNRS 6013, Université de Reims-Champagne-Ardenne, Faculté de Pharmacie, 51, rue Cognacq-Jay, F-51096 Reims Cédex, France


4-Trifluoromethylpyrimidines (2,7) were easily synthesized by reaction of enamino diketones (1,6) with N,N-dimethylguanidine, O-methylisourea or guanidine. The 4,6-bistrifluoromethylpyrimidine (11) was obtained from 10 and O-methylisourea. Hydrolysis of the 2-methoxypyrimidines (2c,7c,12) gave the 4-hydroxypyrimidones (3,8,13).

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2453 - 2462
Published online:
DOI: 10.3987/COM-99-8645
A Convenient Synthesis of (Z)-3- (α-Cyano-α-alkoxycarbonylmethylene)-2-piperazinones and Their Derivatives

Yoichi Yamada,* Heinosuke Yasuda, and Masaaki Kasai

*Utsunomiya University, 350 Mine, Utsunomiya 321-8505, Japan


(Z)-3-(α-Cyano-α-alkoxycarbonylmethylene)-2-piperazinone derivatives (3) and trans-(Z)-3-(α-cyano-α-alkoxycarbonylmethylene)-octahydro-2(1H)-quinoxalinone derivatives (5) possessing various alkoxycarbonyl groups are prepared directly from the reaction of dialkyl (E)-2,3-dicyanobutenedioates (1) with ethylenediamine (2) and with trans-1,2-diaminocyclohexane (4), respectively. Furthermore, cis-1,2-diaminocycloheptane (6) and meso-2,3-diaminobutane (8) were reacted with the diethyl ester 1b to give cis-(Z)-3-(α-cyano-α-ethoxycarbonyl-methylene)decahydro-2H-cycloheptapyrazin-2-one (7) and cis-(Z)-3-(α-cyano-α-ethoxycarbonylmethylene)-5,6-dimethyl-2-piperazinone (9), respectively. The structural studies of 3, 5, 7, and 9 were carried out by NMR experiments in some details.

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2463 - 2470
Published online:
DOI: 10.3987/COM-99-8648
New Chiral 3-Naphthylaminomethylpyrroli- dines: An Unexpected Epimerisation Reaction

Cristiana Fava, Roberta Galeazzi, Giovanna Mobbili, and Mario Orena*

*Dipartimento di Scienze dei Materiali e della Terra, Università di Ancona, Via Brecce Bianche, I-60131 Ancona, Italy


New enantiomerically pure 3-naphthylaminomethylpyrrolidines (8), (9), (14) and (15) were obtained through simple steps starting from chiral 4-ethenylpyrrolidin-2-ones (2) and (3). On the other hand, starting from pyrrolidine (16), an epimerisation reaction occurred, which was explained through formation of the bicyclic ammonium salt (18). Nucleophilic addition of Et2Zn to benzaldehyde, carried out in the presence of 8, gave (S)-1-phenyl-1-propanol in 28% e.e.

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2471 - 2478
Published online:
DOI: 10.3987/COM-99-8661
A Facile and Convenient Synthetic Method for Fluorine-containing 1,2-Dihydropyrido[3,2-h]quinazolines and Pyrido[3,2-h]quinazolines

Etsuji Okada* and Norikado Tsukushi

*Department of Chemical Science andd Engineerring, Faculty of Engineering, Kobe University, Kobe 657-8501, Japan


5,7-Bis(trifluoroacetyl)-8-quinolylamine (1) reacted with various aliphatic and aromatic aldehydes in the presence of aqueous ammonia to afford fluorine-containing 1,2-dihydropyrido[3,2-h]quinazolines (2) and pyrido[3,2-h]quinazoline-6-methanols (3) in moderate to high yields. Dehydrogenation of 2 with DDQ gave the corresponding pyrido[3,2-h]quinazolines (4) in excellent yields. Conversion of alcohols (3) into hydrates (4) with DDQ was also successful.

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Note | Regular issue | Vol 51, No. 10, 1999, pp. 2479 - 2483
Published online:
DOI: 10.3987/COM-99-8668
Synthesis of 4-Benzyl-5-(2,6-dichloro- phenyl)-2-ethoxy-1,2,3,4-tetrahydro-1,4,6,2-oxadiazaphosphorine 2-Oxide

Wynona Johnson,* Alan Faux, and Gary Fallon

*CSIRO, Molecular Science, Praivate BAg 10, Clayton South MDC, Victoria, 3169, Australia


A derivative of the novel heterocyclic ring system - 1,2,3,4-tetrahydro-1,4,6,2-oxadiazaphosphorine (1), was prepared by the cycloaddition of the nitrile oxide generated from hydroximoyl chloride (2) with aminomethylphosphonate (3). The structure was elucidated by NMR analysis and X-Ray crystallography. The stability of the new ring system was investigated.

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Review | Regular issue | Vol 51, No. 10, 1999, pp. 2485 - 2522
Published online:
DOI: 10.3987/REV-99-522
Acetylene-based Functionalized Dihydrofuranones and Related Biomimetic Assemblies

Boris A. Trofimov* and Anastasiya G. Mal'kina

*Siberian Branch, Institute of Chemistry, Russian Academy of Sciences, 1, Favorsky Street, Irkutsk, 664033, Russia


There are overviewed new acetylene-based syntheses of functional dihydrofuran-2-ones and 2-iminodihydrofurans related to naturally occurring and biologically active compounds. Most of the products are synthesized by nucleophilic addition of water, alcohols, amines, azoles, thiols, azide and halogenide ions, etc., as well as multident and multifunctional nucleophiles (thiurea, benzimidazole-2-thione, benzoxazole-2-thione, etc.) to esters, amides or nitriles of α,β-acetylenic γ-hydroxy acids followed by cyclization of the adducts.

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22 data found. 1 - 22 listed